Water-insoluble indoline monoazo dyestuffs



United States Patent 3,347,844 WATER-INSOLUBLE INDOLINE MONOAZO DYESTUFFS Paul Rhyner and Visvanathan Ramanathau, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed June 25, 1964, Ser. No. 378,069 Claims priority, application Switzerland, July 10, 1963, 8,585/63 6 Claims. (Cl. 260-165) ABSTRACT OF THE DISCLOSURE Monoazo dyestuifs are obtained by coupling the diazo compound of an aromatic amine which contains a hydroxyl group, acyloxy group or alkoxy group in orthoposition to the amino group with a trialkyl-Z-methyleneindoline. The azo dyestuffs are useful for dyeing hydroprobic fibers, particularly metal-containing polyolefinic fibers, and exhibit excellent fastness properties.

The present invention is based on the observation that valuable monoazo dyestuffs are obtained when the diazo compound of an aromatic amine, which contains a hydroxyl group, an acyloxy group or an alkoxy group in ortho-position to the amino group, is coupled with a compound of the formula N ilkyl and if the dystuif thus obtained contains an acyloxy or an alkoxy group in ortho-position to the azo group, the acyloxy or alkoxy group is converted into a hydroxyl group.

It is advantageous to use diazo compounds of amines of the formula NHz in which X and Y represent hydrogen or halogen atoms or alkyl, alkoxy, cyano or nitro groups.

As examples there may be mentioned the following amines:

3,347,844 Patented Oct. 17, 1967 The coupling components used are preferably trialkyl- Z-methylene-indolines of the formula Alkyl Alkyl G=CH2 Alkyl in which X and Y represent hydrogen or halogen atoms or alkyl, alkoxy, cyano or nitro groups, for examp 1 :3 :3-trimethyl-Z-methylene-indoline S-methoxy-l :3 3-trimethyl-2-methylene-indoline S-ethoxy-l 3 3-trimethyl-2-methylene-indoline 5-cyano-1 2 3 :3-trimethyl-2-rnethylene-indoline 1-ethyl-3 3-dimethyl-2-methylene-indoline 7-chloro-l 3 3-trirnethyl-2-methylene-indoline S-nitro-l 3 3-trimethyl-2-rnethylene-indoline S-chloro-l 3 3-trimethyl-2-methylene-indoline 6-chloro-1 :3 3-trimethyl-2-methylene-indoline 5 -*iuoro-1 :3 3-trimethyI-Z-methylene-indoline l :3 3-triethyl-Z-methylene-indoline 1:3 3-trimethyl-2-methylene-4:5 and 6:7-benzindoline and 1 :3 3 5-tetramethyl-2-methylene-indoline.

The reaction of the diazo compounds with the hydrocyclic bases is advantageous carried out in an aqueous medium, preferably an acidic medium. It is generally of advantage to buffer excess mineral acid in the course of the reaction with a suitable buffer, for example, sodium acetate, sodium bicarbonate or pyridine. In some cases it can also be advantageous to carry out the reaction in an organic solvent, for example, in glacial acetic acid, pyridine, dimethyl formamide, benzene or acetone.

The water-insoluble dyestuffs obtainable by the process of the invention are new compounds and correspond to the formula in which A represents a radical that is joined to the azo group through a carbon atom, the said carbon atom being linked, either directly or through a further carbon atom, with a hetero cyclic nitrogen atom, and B represents an aliphatic, a hydroaromatic, an aromatic or a heterocyclic radical which contains a hydroxyl group or an enolizable keto group in ortho-position to the azo group. The dyestuffs advantageously do not contain further hydroxyl groups in addition to the hydroxyl group in ortho-position to the azo group.

Of special interest are dyestuffs of the formula Alkyl in which D represents the atomic grouping required to closea five membered or a six membered heterocyclic ring,'and B represents a benzene radical that contains a hydroxyl group in ortho-position to the azo group, and especially those of the formula in which X, Y, X and Y represent hydrogen or halogen atoms or alkyl, alkoxy, cyano or nitro groups.

When the dyestuffs obtained contain an acyloxy or alkoxy group in ortho-position to the azo group, they are converted into ortho-hydroxy dyestuffs by a treatment with an acid or an alkali hydroxide.

The new dyestufis are suitable for dyeing hydrophobic fibers, especially polyolefines containing metal, preferably nickel. Metal-modified polyolefines generally contain metal compounds in amounts of 0.05 to 2% as protection against ultra-violet irradiation, the said metal compounds being, for example, copper or zinc compounds, but preferably nickel salts, for example, nickel stearate, nickel acetate or nickel thiocarbamate.

In the dyeing process, the aforementioned dyestuffs are advantageously used in a state of fine division, and dyeing is carried out in the presence of a dispersing agent, for example, soap, sulfite cellulose waste liquor or a synthetic detergent, or in the presence of a combination of various wetting and dispersing agents. Prior to dyeing, it is generally of advantage to convert the dyestufi to be used into a dyeing preparation that contains a dispersing agent and finely divided dyestufi in a form such that a fine dispersion is formed when the said preparation is diluted with water. Such dyestutf preparations may be made in known manner, for example, by reprecipitating the dyestuff from sulfuric acid and grinding the suspension thus obtained together with sulfite cellulose waste liquor or, if necessary, by grinding the dyestufi in a highly efiicient grinding device in the dry state or wet state in the presence or absence of a dispersing agent.

Dyeing is advantageously carried out in an aqueous dispersion at the boil and in the presence of a wetting agent. It has been found advantageous to render the dyebath slightly acid, for example, by the addition of a weak acid, for example, acetic acid. It must be assumed that, during the dyeing process, the dyestuff reacts with the metal compounds present in the fiber to form a metal complex.

In addition to application by the exhaustion process, the above-mentioned dyestuffs may also be applied in accordance with the process of the invention by padding and printing. In printing, for example, a printing paste is used that contains the finely divided dyestufi in addition to the usual printing assistants, for example, wetting agents and thickenings.

The process of the present invention yields strong, full dyeings and prints possessing excellent properties of fastness, to light, to dry cleaning, to sublimation during storage, and to rubbing. The dyestufis exhibit exceptional tinctorial strength and ensure excellent preservation of wool.

The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

Example 1 5.4 parts of 1:3:3-trimethyl-2-methylene-indoline are dissolved in a mixture comprising 4.5 parts by volume of hydrochloric acid of 30% strength and 30 parts of water. A diazo suspension prepared in the customary manner from 4.6 parts of S-nitro-Z-arninophenol is then added grdaually at O to C. parts of pyridine are added dropwise to complete coupling. After a number of hours, the dyestutf suspension is filtered and the filter residue is washed with water and dried. The dyestuif of the formula is obtained in the form of a dark red powder. It dyes nickel-containing polypropylene claret tints possessing a high degree of fastness to light and to dry cleaning.

In Column II of the following table there are listed a number of further dyestulfs that are obtained when the appropriate amino-hydroxy-benzenes or naphthalenes are coupled with the appropriate 1:3:3-trialkyl-2-trialkyl- 2-methylene-indolines. In Column III there are listed the tints obtained with these dyestuffs on nickel-containing polypropylene; the dyeings possess a good fastness to light and to dry cleaning.

N o. Dyestufi Tint 1 H C\ /0 H3 Scarlet.

OH C

N=NC r-r='o l CH3 N 0 z 2 HaC /-C Ha Claret.

O H C OzN- N=NC H=C III CH3 CH3 3 H3C\ /CH3 Scarlet.

OH C

N=N-CH=C III C H; Cl

4 0H H3C\ /CH3 DO.

| o 01 N=NC H=O\ y III 1 CH3 Cl 6 H3C\ /0 H Claret.

CH C

N=NCH=C O2N CH3 6 EsC\ /CH3 Red.

0 H i o N=NC H=C i CH C N 7 H3C\ /CHa Claret.

O H C l N=NC H: C OzN hll 0 Ha C1 No. Dyestufl Tint 8 HaC\ /CHa Red.

OH C

I NO,

N=NCH=C (in CH3 9 vHsC\ /CH3 Red.

OH C l -ooH3 --N='N-CH=C\ I (In CH:

10 E30 /CH3 Red brown.

N= N-C =o\ i I OH: 01

11 H3C\ /CH3 Scarlet.

OH O i -o1 -N=NCH=C 1|3 CHa 12 HaC CH3 Orange.

OH C N=N- CH=C I CH3."

13 H3C\ /.CHa Scarlet. O'Hf C I N=NCH=C f CH3 14..." E30 CH3 Scarlet.

OH C N=N-CH=C G1 CH3 15 E 0 CH3 Scarlet.

OH C I N=NCH=C\ I CH3 N01 No. Dyestufi Tint 16 H3O CH Mauve.

NC N==NCH=O 0H If CH3 17 Gina /CH; Scarlet.

OH 0 I N=N-OH=C\ i l (EH5 o1 Example 2 1 part of an aqueous paste of the dyestuff of the formula H3C\ /OH; 0 V C=CHN=NNO= I I I 0H and approximately 1 part of dried sulfite cellulose waste liquor or some other suitable dispersing agent are ground to a fine paste in a roller mill, the paste thus obtained having a dyestuifcontent of 10%.

100 parts of nickel-containing polypropylene are washed for half an hour in a bath containing 1 to 2 parts of the sodium salt of N-benzyl,u-heptadecyl'benzimidazole disulfonic acid per 1000 parts of Water. The material is then entered into a dyebath containing 10 partsof the dyestuif paste obtained as described in the preceding paragraph, 3 parts of the sodium salt of N-benzyl-p-heptadecylbenzimidazole disulfonic acid and 1 part of acetic acid of 40% strength per 2000 parts of water. The dyebath is kept at the boil for 1 hour, whereupon the dyed material is rinsed and dried. A claret dyeing possessing a high degree of fastness to light and to dry cleaning is obtained.

Example 3 1 part of an aqueous paste of the dyestuif of the formula H3C\ /OH; 7 o 01 o1 C=CHN=N and approximately 1 part of 1:1'-dinaphthaylmethane- 2:2-disulfonic acid are ground to a fine paste in a roller mill, the, paste thus obtained having a dyestuif content of 10% are then mixed by means of a high-speed stirrer. A nickel- 2. The dyestufi of the formula containing polypropylene fabricis printed with the .print- H30 ing paste thus prepared. The printed fabric is dried,

steamed for 30 minutes, rinsed in cold water for min C utes, centrifuged, and then treated for lO minutes at 60 C. with a solution containing 2 grarnsof the condensation product of 9 mols of ethylene oxide and 1 -mol of nonyl O N phenol per liter of water. A scarlet dyeing possessing very 2 T I good properties of fastness is obtained. H:

10 3. The dyestuif'of' the 'formula Example 4 Z-para-toluene-sulfonylhydroxyaniline is diazotised in OH 6 the customary manner and the diazo compound thus obl tained is added to a solution of 5-chloro-1:3:3-trimethyl- N=NCI-I=O Z-methylene-indoline in hydrochloric .acid. Coupling is completed by the addition of sodium actate, 24 parts of the i N azo 'dyestuif so obtained are dissolved in 200 parts of (3H3 alcohol, and then 90 parts of an aqueous solution contain- 01 ing parts of sodium hydroxide are added. The solution 20 4 h d t ff f the f l is boiled under reflux. When the toluene sulionyloxy group has been completely hydrolysed, the mixture is neutralized, the alcohol is distilled off, the dyestutf suspension is OH O filtered and the filter residue is washed with water and v dried. The dyestufi so obtained dyes nickel-containing 25 N=N CH=C polypropylene scarlet tints possessing a high degree of fastmess to light and to dry cleaning. N

Example 5 5. The dyest-uif of the formula Diazotized ortho-anisidine is coupled vwith S-chloro- 3O H 0 1:3:3-trimethyl-Z-methylene-indoline. 34 parts of the 2120 OH \C/ dyestuff thus obtained, 500 parts of hydrorbromic acid of v OOH 63% strength and 100 parts of glacial acetic acid are N=N CH=C heated to approximately 115 C. When the methoxy group has been completely demethylated, the mixture is neu- N tralized, the dyestutf is isolated 'by filtration, washed with I a water and then dried. The dyestufi thus obtained is iden- 01 a tical with the dyestuffobtained in the manner described in 6 The dyestuff of the formula Example 4. 40 i What is claimed is: H 1. A water insoluble monoazo dyestu'ff of the formula 0H Y UNITED STATES-PATENTS Alkyl 2,815,338 12/1957 Rue gg 260-167X FOREIGN PATENrs in which X1 nd Y each represents a member se- 647876 9/1962 Canada lected from the group consisting of hydrogen, halogen, CHARLES PARKER primary Examiner lower alkyl, lower alkoxy, cyano and nitro and Alkyl represents lower alkyl. t @WGAAWM E m' a- 

1. A WATER INSOLUBLE MONOAZO DYESTUFF OF THE FORMULA 